Aqueous dispersion of montan wax and other water-immiscible bodies and process of making



AQUEQUS EESPERSION @F PEONTAN 'WAX AND {EL-THEE WATER-EMMISCKELE BQDEES AND F lt IAKENG Oscar I Neltske, ilainoridg-e, Mass, assignor to Bennett, incorporated, East Cambridge, Mass, a corporation of Massachusetts No Drawing. Application December 7, 1929 Serial No. 412,580

9 Claims. (Cl; 1391-4) This invention relates to the production of persions oi mixtures-oi Montan Wax and thermoaqueous' dispersions of Montan Wax and other plastic hydrocarbon bodies such as asphalt water-immiscible bodies. While not limited and/or pa run, but in such case, too, it is neces thereto, this invention deals. more specifically sary to use dilute solutions of alkali to produce 5 with the dispersion in water of lviontan wax and concentrated, free-flowing, aqueous dispersions so those water-immiscible bodies which are therof high stability and capable of being diluted moplastic hydrocarbons, by which expression to any desired consistency by the mere addition is meant the asphalts, the paraffins, and analoof water thereto. 7 j gous chemically inactive bodies which are solid In preparing the aqueous dispersions of the 0 under usual atmospheric temperature condipresent invention, the Montan was alone or a tions, but are capable of being melted suhstan- 'mixture of the Montan war; with asphalt and/0r tially without decomposition under the appliparaffin is heated to above its melting point, and cation of heat. a dilute solution of alkali inheated condition An object of the present invention is the is added thereto and mixed therewith. The mix- 15 production of stable aqueous dispersions of ing or" the molten material and the solution of Montan wax and thermoplastic hydrocarbon alkali may be eiiected in batches, or each of bodies of high dispersed solids content and of these materials may be withdrawn at the deuniformly fine particle size. Another object is sired rate from independent batches, as. conto produce dispersions of this character haying tinuously flowing streams, and the I streams 2 the capacity of being readily diluted with water united and intimately mixed. The, solution of to an extremely low solids content without suoalkali is preferably at a temperature sufficiently stantial agglomeration and coalescence of the high so that when mixed with the molten therxdispersed particles or separation thereof. from moplastic material, the resultant temperature the aqueous medium. I have discovered that it will be higher than that necessary to maintain 25 is possible to producedispersions of lviontan wax the thermoplastic material molten, as under and thermoplastic hydrocarbons having the such conditions it is possible to effect a disdesired characteristics, by the use of dilute solupersion of, the molten mass i to uniformly fi tions of alkali, for instance, caustic soda soluparticles without premature congealing of the tions up to about 2% strength, or solutions of molten material. It is possible, however, to I 39 ther alkalies such caustic potash, sodium arrive at the same results byheating the thermocarbonate, and ammonia of corresponding norplastic material and the solution together to mality. When solutions of caustic soda or, say, temperatures above the melting point of the maabout 1% or lower strengths are used, the re terial and then effecting an intimate mixture, suiting dispersions are free-flo ing, even when In producing dispersions of paraiiln, it is 35 theysometimes contain as 50% dispreferable to chill the dispersion immediately v persed solids and are capable oi being greatly after its formation and While the dispersed pardiluted with water, for ins ance, to a solids contic es of paraffin are in molten condition, since tent of about 2% or less, without noteworthy if such a dispersion is permitted to cool slowe agglomeration coalescence of the dispersed ly, the fine particles Of paramn te 130 agglom- 40 particles. The use dilute solut one or alkali crate orcoalesce while in the liquid state. The

' in producing the ded dispersions is an es desired chilling effect may be obtained by carrysential feature of my invention, for if it be ating out the mix and dispersing operation in tempted to produce such concentrated disperapparatus provided with a jacket through which sions with solutions of caustic soda much above cold water or other cooling medium may he 45 2% strength, the resulting product is a semipassed to congeal rapidly the fine particles of solid which cannot readily be diluted with water, molten paraiiin before they have opportunity but from which part or" the water phase may to agglomerate and coalesce. be squeezed by applying moderate hand pres- In accounting for the surprising results which sure thereto. Evidently the water is present I secure, one must look to the composition of 50 therein in the form of water of hydration of the Iviontan wax and ascertain What chemical some kind, analogous, for examp e, to action may take place beween the Wax and a water of hydration of some crystal ed salts or solution of alkali under various conditions. the water of absorption of colloids such as glue. This Wax, as well known, varies more or less,. My discovery may be advantageously applied depending upon its origin and method of ex- 55 to the preparation of commercially valuable distraction, but all varieties consist generally of 'Gll I by prolonged a mixture of fatty acids known as crude montanic acid and unsaponiflable constituents which are supposed to be saturated hydrocarbons. The crude montanic acid is said to comprise, in the main, pure montanic acid having the formula CzsHseOz, and a smaller amount of fatty acid of lower molecular weight. A dilute solution of alkali reacts upon and saponifles the more readily saponifiable content of the Montan waxprobably the fatty acids of lower molecular weight-to produce soaps of .high stability and hence capable of stabilizing the resulting dispersion even when present in traces, as when the dispersion is diluted with water. Only a portion of the alkali of the dilute solution is consumed in saponifying the more readily sapon-..

ifiable portion of the Montan wax, as the more difliculty saponifiable portion is saponified only cooking with concentrated solutions of alkali. When concentrated solutions of alkali are employed without prolonged cooking and in amount to produce a product-of high solids content, the product is of exceedingly high residual alkalinity, and this highly alkaline condition evidently favors some kind of hydration or crystallization of the soap constituents, much in-the same way that the presence of caustic soda in sodium silicate solutions under certain conditions favors crystallization into silicates having water of crystallization, whereas neutral silicate solutions have no crystallizing tendencies.

It is easier to disperse crude l /lontan wax than 1 refined Mon'tan wax. The explanation for this, aside from the fact that the crude Montan wax contains traces of material which may have the function of protective colloids, seemsto lie in its much larger content of material having hydroxyl groups, which may react in part with the dilute solution of alkali to form stable soaps. Thus, the ester number, which is a measure of hydroxyl groups, may be 35 in the case of a crude Montanwax and only 2 in the case of a refined Mcntan wax of similar origin, these being the values of the well-known Riebeck variety. In the case of both crude and refined Montan wax, however, stable soaps or other saponification products are formed with the more readily saponifiable constituents, these products serving as the stabilizers or protective colloids in the resulting dispersions.

There are important advantages which are realized by using Montan wax as a constituent in forming dispersions of asphalt and/or paraffin. Not only is it possible to produce dispersions of the desired characteristics, but their production involves the expenditure of .little energy and the use of exceedingly small amounts of alkali, as very little soap need be produced. The resulting dispersion, being of high solids content, may be stored or shipped with low water content and may then'be readily diluted to the consistency desired for use.

I shall now give specific examples of procedure according to which dispersions such as described may be produced and illustrative uses to which they may be put. In the case of lvfontan wax-asphalt dispersions, it is desirable from a cost standpointto use as little Montan wax as possible, since even the crude Montan wax is much more expensive than most types of asphalt. I have found that as little as about 10% to 15% of crude Montanwax need be used to furnish sufiicient protective colloid in the product. Assuming that the asphalt'is air-blown and has a melting point of 150 F. (ball and the molten mixture is' added approximately 65' parts of a solution of caustic soda at a temperature of 150 F. The melted mixture and solution are preferably maintained under rapid agitation as they are mixed, so as to effect a rapid and uniform tion' throughout the mass and thus to promote uniform chemical reaction and dispersion. Inasmuch as the spec fic heat of the molten mix ture is much less than that of water, little, if any, liberation of steam takes place at the final temperature produced, which is above the melting point of the thermoplastic materials but below the boiling point of water. The resulting dispersion is of a creamy consistency, so that water may be added and readily distributed therethrough in large quantities. Itis composed of uniformly fine particles in the order of dissemination of the solumagnitude of 1/5080 to M16000 of an inch in 7 diameter and is characterized by its stability even at as low as 1% solids content. Such a dispersion is suitable for use as a paint, at a solids content of about 30%, under which conditions it has remarkably good covering power and is comparable in this respect to the so-called asphalt paints preparediby dissolving asphalts in organic solvents. Such paints maybe applied with the usual paint brushes and may set under usual'rooin temperature conditions, say, 70 F.,

as continuous films in about an hour. The dis-' persion is suitable for use in the impregnation of felts, papers, yarns, textile fabrics, and the like, to render them waterproof. It is an excellentsize for paper pulp intended more especially for the production of waterproof papers,

as the resulting papers are free from the unsightly asphalt specks appearing when the usual asphalt dispersions'are employed. Evidently the usual asphalt dispersions when added to a dilute aqueous pulp suspension undergo premature pre-' from that incident to dilution of some dispersions with water is produced. a

A papermaking procedure designed for the production of a mulch paper using the asphalt dispersion product of the present invention may be practised substantially as follows. A suitable stock, such as kraft pulp,'may be, beaten out to the desired degree of hydration, say, from one to four hours, whereupon the desired amount of .Montan wax-asphalt dispersion may be added thereto, say from 10% to 20%, based on the weight of dry pulp. After the dispersion has been uniformly disseminated throughout the pulp, about i% to 6% alum, based on the weight of dry pulp, may be added to effect a fixation of the dispersed particles on the fibers. When the sized pulp is then run out on a paper machine, the white water removed during papermaking operations is substantially clear, showing that substantially all the size been retained by the fibers; Moreover, because of the fine particle size, no gumming of the wires or felts is encountered during the papermaking operation.

" suitable for The resu ting paper isadmirably adapted for use as a mulch, being highly waterproof because oi the uniform distribution of waterproofing material therethrough. Rather than having a black color, the paper has a tan shade, which indicates that the asphalt has been distribute resulting disperson is of. a creamy consistency and is sufficiently fluid to be sucked up with a pipette. The finaldispersion, in a case when a caustic solution is used, may contain as high as 50% of the alkali originally used in free condition. Preferably the resulting paraffin dispersion, while at a temperature above that of the melting point of the para-din, i suddenly chilled, as the fine particles of 'p'ranin have tendency to agglome'ate and coalesce while in the liquid state, if allowed to cool slowly. The

resulting dispersion is, as in the case of the asphalt dispersion, an excell nt 'waterproofing composition for felts, papers, yarns, textiles, fabrics, or the like. It is adapted for use on the calender rolls of a paper machine, to impart a high gloss or finish to the paper, under which conditions it may be used at Very low concentration and maintain its stability. It is also the sizing of paper pulp in the beater engine an for the so-called tub-sizing of paper to render it waterproof and to impart thereto the appearance and character' -tics of waxed papers produced by dipping in molten paraffin. In sizing pap rs after they have been formed by passing through a bath of the c fin dispersion, the paper be either 121 terleaf condition or in partially sized condition, in which latter case when passed through the para-fin wax dispersion too great an absorption of paraffin wax will not take In preparing dispersions of the type herein'oefore described, one should determine n the case of each particular dispersion dis persed solids concentration at which the disperion is f ee-flowing and dilutacle h water when the proper small amount of alxai is used in solution for saponifying the readily saponifiable portion of the lfontan wax. It is also necessary to use a sufilcient amount of -iontan wax to furnish suilficient saponiiiable constituent to result in a stable dispersion, but in the of both the paraifins and asphali's, only about 10% to 15% of crude Morita-n wax is necessary for this purpose, although it may be necessary to use as high as 26% to 25% of the refined Montan wax. In the case of the parafiin dispersions made with such an amount of al ii to ensure no solidifying tendenciel the socontent should not be above 50% to 66%, and tie case of the asphalts of a melting point of I F., not above 36% to 40% solids con nt for the best results. If these solids contents are exceeded, the normal condition of the be solid and diluting water v be incorporate therein only with great di iculty and with the expenditure of considerable energy. The proporcaustic soda of tionsof the various materials, as stated herein,

are by way of example only, variations being contemplated therein, within the principles stated above.

The strength of the caustic soda solution used in preparing dispersions of paraffin and Montan wax of about 50% to 60% dispersed solids content and comprising 85 parts by weight of parafiin and 15 parts of crude Montan wax should not be above about or belowabout 4%, at which lower limit of alkalinity the resulting dispersions would be. unstable upon dilution with water, and dispersed solids would fiocculate or separate out. 'On the other hand, the strength of the caustic soda solution may be as highas 1% in the case of dispersions of asphalt and li lontan wax of about 35% to 40% solids content and comprising 85 parts by weight of asphalt and 15 parts of Montan wax. lhese strengths of caustic soda solution should be the same when refined Montan wax is used in lieu of the crude wax, but, as previously stated, the proportion of Montan wax relative to the other thermoplastic material must be increased in order to produce a stable product. The strength of the caustic soda solution may be increased somewhat, to produce satisfactory dispersions, if the solution is used in suliiciently greater proportion than those given, but, inasmuch as this expedient leads to dispersions of lower than maximum solids contents, it is generally undesirable.

I claim:

1. An alkaline aqueous dispersion whose solids content consists substantially of Montan wax, a normally solid asphalt, and the saponification products resulting from the reaction of an alkali with a portion of the saponifiable content of the wax, said dispersion being of sufficiently low alkalinity to be free-flowing and being substantially free from stabilizing agents other than said saponiiication products.

2. An alkaline aqueous dispersion whose solids content consists substantially of a relatively small amount of Montan Wax, a large amount of a.

normally solid asphalt, and the saponification, products of a portion of the saponifiable content of the Wax, said dispersion being of sufficiently low alkalinity to be free-flowing and being substantially free from stabilizing agents other than said saponification products.

3. A process which comprises intimatelymixing a molten mixture of Montan wax and as phalt with a solution of a non-stabilizing alkali, of less than 1% concentration, to produce a free-flowing dispersion of the unsaponified constituents of the molten mixture in the aqueous medium.

i. A process which comprises intimately mix-' ing a solution of caustic soda of less than about 2% strength with a molten mixture oia-comparatively small amount of Montan wax and a large amount of'a normally solid asphalt to the wax and to eilect a dispersion of the ,un saponiiied constituents of the molten mixture in the aqueous medium containing said saponi .saponify a portion of the saponifiable content of fied products as substantially the only stabilizing agents of the dispersion.

5. A dispersion of a mixture consisting of M asphalt, Montan wax and a stabilizing agent 6. A dispersion of particles comprising a mixture of asphalt and Montan wax supported in .an aqueous alkaline medium and embodying re-I .an alkali, such as, caustic soda, with molten Montan Waxas the stabilizing agentof a dis-' action products produced by-the action-of said alkali on said Montan Wax, said reaction products constituting substantially the only stabilizing agents of the dispersion.

7. A dispersion consisting of asphalt and reaction products resulting from the reaction of persion embodying dispersed particles of said asphalt supported. in an aqueous medium. I V

8. The process of forming adispersion of asphalt particles supported in an aqueous medium comprising. melting and mixing together asphalt with a smaller quantity of Montan Wax to form the melt and saponifying a portion of the saponifiable material in said wax for stabilizing said dispersion substantially only with said saponification products by dispersing said melt in an alkaline aqueous solution of less than 1% concentration while maintaining the melt and solution'in a state of agitation and at an ele- 

